This invention relates to novel compositions of matter which are highly effective as catalyst components, and to the preparation and use of such compositions.
Partially hydrolyzed aluminum alkyl compounds known as aluminoxanes (a.k.a. alumoxanes) are effective in activating metallocenes for polymerization of olefins. Activating effects of water in such systems were initially noted by Reichert, et al. (1973) and Breslow, et al. (1975), and extended to trimethylaluminum-based systems by Sinn, Kaminsky, et al. (1976). Subsequent research by Sinn and Kaminsky demonstrated that this activation was due to formation of methylaluminoxane from partial hydrolysis of trimethylaluminum present in the system. Methylaluminoxane. (a.k.a. methylalumoxane) has become the aluminum co-catalyst of choice in the industry.
Subsequent to the above original discoveries in this field, considerable worldwide effort has been devoted to improving the effectiveness of catalyst systems based on use of aluminoxanes or modified aluminoxanes for polymerization of olefins and related unsaturated monomers.
Representative of many patents in the field of aluminoxane usage in forming olefin polymerization catalyst systems with suitable metal compounds is U.S. Pat. No. 5,324,800 to Welborn et al. which claims an original filing date in 1983. This patent describes olefin polymerization catalysts made from metallocenes of a metal of Groups 4b, 5b, or 6b, and a cyclic or linear C1-C5 alkylaluminoxane. The cyclic and the linear aluminoxanes are depicted, respectively, by the formulas (Rxe2x80x94Alxe2x80x94O)n and R(Rxe2x80x94Alxe2x80x94O)nAlR2 where n is from 1 to about 20, and R is most preferably methyl. The aluminoxanes are made by controlled hydrolysis of the corresponding aluminum trialkyl.
Another relatively early patent in the field, U.S. Pat. No. 4,752,597 to Turner based on a filing date of 1985, describes olefin polymerization catalysts comprising the reaction products of a metallocene complex of group IVB, VB, VIB, and VII of the periodic table and an excess of aluminoxane. These catalysts are formed by pre-reacting a metallocene and an aluminoxane in mole ratios greater than 12:1, such as about 12:1 to about 100:1, to produce a solid product which precipitates from solution. Despite assertions of suitable catalytic activity, in reality the activity of these materials is so low as to be of no practical importance whatsoever.
In U.S. Pat. Nos. 4,960,878 and 5,041,584 to Crapo et al. modified methylaluminoxane is formed in several ways. One involves reacting a tetraalkyldialuminoxane, R2Alxe2x80x94Oxe2x80x94AlR2, containing C2 or higher alkyl groups with trimethylaluminum (TMA) at xe2x88x9210 to 150xc2x0 C. Another involves reacting TMA with a polyalkylaluminoxane (xe2x80x94Al(R)xe2x80x94Oxe2x80x94)n where R is C2 alkyl or higher and n is greater than 1, e.g., up to 50. Temperatures suggested for this reaction are xe2x88x9220 to 50xc2x0 C. A third way involves conducting the latter reaction and then reacting the resultant product, which is indicated to be a complex between trimethylaluminum and the polyalkylaluminoxane, with water. The patent states that the water-to-aluminum ratios used to make the polyalkylaluminoxane reagent have an effect on the activity of the final methylaluminoxane. On the basis of ethylene polymerizations using zirconocene dichloride catalyst and a complex of trimethylaluminum with polyisobutylaluminoxane subsequently reacted with water (MMAO) as co-catalyst, it is indicated in the patent that the highest polymerization activities were achieved with MMAO co-catalyst prepared at H2O/Al ratios of about 0.6 to about 1.0 and Al/Zr ratios in the range of 10,000/1 to 400,000/1.
Various references are available indicating that isobutylaluminoxanes themselves are relatively ineffective on their own as co-catalysts. For example, several other reactions of alkylaluminum compounds with water are disclosed in U.S. Pat. Nos. 4,960,878 and 5,041,584. Thus in Example 1 of these patents, DIBAL-O (tetraisobutyldialuminoxane), a commercial product, was prepared by reaction of water with triisobutylaluminum (TIBA) in heptane using a water/TIBA ratio of about 0.5, followed by solvent stripping at 58-65xc2x0 C. under vacuum. In Examples 3-6 of the patents isobutylaluminoxane (IBAO) was prepared by controlled addition of water to a 25% solution of TIBA in toluene in the temperature range of 0-12xc2x0 C., followed by heating to 70-80xc2x0 C. to ensure complete reaction and remove dissolved isobutane. H2O/Al ratios used were 0.98, 1.21, 1.14, and 0.88. IBAO was again made in a similar manner in Example 52 of the patents. Here the H2O/Al ratio was 0.70, and the product was heated at 75xc2x0 C. And in Example 70 tri-n-butylaluminum (TNBA) in toluene was treated at 0-10xc2x0 C. with water followed by heating to 85xc2x0 C. Ethylene polymerizations using zirconocene dichloride catalyst and various products from the foregoing Examples were conducted. Specific activities (xc3x97103 gPE/(gZr.atm C2H4.hr)) of the catalysts made with DIBAL-O from Ex. 1, IBAO from Ex. 3, and IBAO from Ex. 6 were, respectively, 4.1, 4.2, and 7.7, as compared to 1000 for the catalyst made using conventional MAO as the co-catalyst. The patents acknowledge that tetraisobutyldialuminoxane (DIBAL-O) showed xe2x80x9cpoor polymerization activityxe2x80x9d, and from the foregoing test results the same can be said to apply to IBAO.
WO 96/02580 to Dall""occo, et al. describes olefin polymerization catalysts made by contacting a metallocene of Ti, Zr, or Hf, an organoaluminum compound having at least one specified hydrocarbon substituent on the xcex2-carbon atom of an aliphatic group bonded to an aluminum atom, and water. Various ways of bringing these components together are suggested. Polymerizations described were carried out using Al/Zr mole ratios ranging from 500 up to as high as 5000.
EP 0 277 004 to Turner, published in 1988, describes the successful preparation and use as catalysts composed of an ionic pair derived from certain metallocenes of Group 4, most preferably bis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafnium dimethyl, reacted with certain trisubstituted ammonium salts of a substituted or unsubstituted aromatic boron compound, most preferably N,N-dimethylanilinium tetra(pentafluorophenyl)boron. While EP 0 277 004 mentions that compounds containing an element of Groups V-B, VI-B, VII-B, VIII, I-B, II-B, III-A, IV-A, and V-A may be used in forming the catalysts, no specific compounds other than boron compounds are identified. In fact, EP 0 277 004 appears to acknowledge inability to identify specific compounds other than boron compounds by stating: xe2x80x9cSimilar lists of suitable compounds containing other metals and metalloids which are useful as second components could be made, but such lists are not deemed necessary to a complete disclosure.xe2x80x9d See in this connection Hlatky, Turner and Eckman, J. Am. Chem. Soc., 1989, 111, 2728-2729, and Hlatky and Upton, Macromolecules, 1996, 29, 8019-8020.
U.S. Pat. No. 5,153,157 to Hlatky and Turner states that its process xe2x80x9cis practiced with that class of ionic catalysts referred to, disclosed, and described in European Patent Applications 277,003 and 277,004.xe2x80x9d The process of U.S. Pat. No. 5,153,157 involves forming an ionic catalyst system from two components. The first is a bis(cyclopentadienyl) derivative of a Group V-B metal compound containing at least one ligand which will combine with the second component or portion thereof such as a cation portion thereof. The second component is referred to as an ion exchange compound comprising (1) a cation which will irreversibly react with a ligand of the Group IV-B metal compound and (2) a noncoordinating anion which is bulky, labile, and stable. The second component, also termed an activator component, comprises compounds of Groups V-B, VI-B, VII-B, VIII, I-B, II-B, III-A, IV-A, and V-A identified by a general formula. Besides referring to the boron compounds of EP 277,004, supra, such as tri(n-butylammonium)tetra(pentafluorophenyl)boron and N,N-dimethylanilinium tetra(pentafluorophenyl)boron as suitable activators, the U.S. ""157 patent teaches use of boron compounds having a plurality of boron atoms, and also trialkyl aluminum compounds, triaryl aluminum compounds, dialkylaluminum alkoxides, diarylaluminum alkoxides, and analogous compounds of boron. Of the organoaluminum activators triethylaluminum and trimethylaluminum are specified as most preferred. The Examples show use of a catalyst system formed from (1) a solution of bis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafnium dimethyl and N,N-dimethylanilinium tetra(pentafluorophenyl)boron together with (2) triethylborane, triethylaluminum, tri-sec-butylborane, trimethylaluminum, and diethylaluminum ethoxide. In some cases the catalyst formed from the metallocene and the N,N-dimethylanilinium tetra(pentafluorophenyl)boron without use of a compound of (2) gave no polymer at all under the polymerization conditions used.
U.S. Pat. No. 5,198,401 to Turner, Hlatky, and Eckman refers, in part, to forming catalyst compositions derived from certain metallocenes of Group 4, such as bis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafnium dimethyl, reacted with certain trisubstituted ammonium salts of a substituted or unsubstituted aromatic boron compound, such as N,N-dimethylanilinium tetra(pentafluorophenyl)boron or tributylammonium tetra(pentafluorophenyl)boron as in EP 0 277 004. However here the anion is described as being any stable and bulky anionic complex having the following molecular attributes: I) the anion should have a molecular diameter about or greater than 4 angstroms; 2) the anion should form stable salts with reducible Lewis acids and protonated Lewis bases; 3) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; 4) the anion should be a relatively poor nucleophile; and 5) the anion should not be a powerful reducing or oxidizing agent. Anions of this type are identified as polynuclear boranes, carboranes, metallacarboranes, polyoxoanions and anionic coordination complexes. Elsewhere in the patent it is indicated that any metal or metalloid capable of forming a coordination complex which is resistant to degradation by water (or other Brxc3x8nsted or Lewis acids) may be used or contained in the second activator compound [the first activator compound appears not to be disclosed]. Suitable metals of the second activator compound are stated to include, but not be limited to, aluminum, gold, platinum and the like. No such compound is identified. Again after listing boron compounds the statement is made that xe2x80x9cSimilar lists of suitable compounds containing other metals and metalloids which are useful as second components could be made, but such lists are not deemed necessary to a complete disclosure.xe2x80x9d In this connection, again note Hlatky, Turner and Eckman, J. Am. Chem. Soc., 1989, 111, 2728-2729, and Hlatky and Upton, Macromolecules, 1996, 29, 8019-8020.
Despite the above and many other efforts involving aluminum co-catalysts, the fact remains that in order to achieve suitable catalysis on a commercial basis, relatively high aluminum to transition metal ratios must be employed. Typically for optimal activity an aluminum to metallocene ratio of greater than about 1000:1 is required for effective homogeneous olefin polymerization. According to Brintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, 34 1143-1170:
xe2x80x9cCatalytic activities are found to decline dramatically for MAO concentrations below Al:Zr ratio roughly 200-300:1. Even at Al:Zr ratios greater than 1000:1 steady state activities increase with rising MAO concentrations approximately as the cube root of the MAO concentrationxe2x80x9d.
This requirement of high aluminum loading is mainly caused by a metallocene activation mechanism in which generation of catalytically active species is equilibrium driven. In this role MAO acts as a Lewis acid to remove by group transfer a leaving group Xxe2x8ax96 from the transition metal. This forms a weakly-coordinating anion, MAO-Xxe2x8ax96, in the corresponding transition metal cation. That is, in such systems the following equilibrium exists: 
The Lewis acid sites in MAO abstract a negatively charged leaving group such as a methide group from the metallocene to form the catalytically active ion pair. The activation process is reversible and Keq is typically small. Thus the ion pair can return to its neutral precursors which are catalytically inactive. To overcome this effect, a large excess of MAO is required to drive the equilibrium to the right.
The high aluminum loadings required for effective catalysis in such systems result in the presence of significant levels of aluminum-containing residues (xe2x80x9cashxe2x80x9d) in the polymer. This can impair the clarity of finished polymers formed from such catalyst systems.
A further disadvantage of MAO is its limited solubility in paraffinic hydrocarbon solvents. Polymer manufacturers would find it of considerable advantage to have in hand aluminoxane and metallocene-based materials having high paraffin solubility.
Still another disadvantage of MAO has been its relatively high cost. For example, in an article entitled xe2x80x9cEconomics is Key to Adoption of Metallocene Catalystsxe2x80x9d in the Sep. 11, 1995 issue of Chemical and Engineering News, Brockmeier of Argonne National Laboratory concluded that xe2x80x9ca reduction in costs or amount of MAO has the potential for greatly reducing the costs to employ metallocene catalystsxe2x80x9d.
Thus it would be of inestimable value to the art if away could be found of providing catalyst components based on use of aluminoxanes that are effective co-catalysts for use with transition metal compounds at much lower aluminum:metal ratios than have been effective heretofore. In addition, the art would be greatly advanced if this could be accomplished with aluminoxane compositions that are less expensive than MAO, that have high solubility in paraffinic solvents and that produce lower ash residues in the polymers.
The invention described and claimed in U.S. Pat. No. 6,160,145 is deemed to have fulfilled most, if not all, of the foregoing desirable objectives. In brief summary, that invention makes it possible to provide catalyst compositions in which a low cost co-catalyst can be employed at very low Al loadings. Such catalyst compositions typically have high solubility in paraffinic solvents. Moreover they yield reduced levels of ash and result in improved clarity in polymers formed from such catalyst compositions. Making all of this possible is the provision of a compound which comprises (i) a cation derived from a transition, lanthanide or actinide metal compound, preferably a metallocene, by loss of a leaving group, and (ii) an aluminoxate anion (a.k.a. aluminoxanate anion) derived by transfer of a proton from a stable or metastable hydroxyaluminoxane to said leaving group. In contrast to aluminoxanes used prior to the Parent Application and acting as Lewis acids (Eq. 1), the present compositions utilize hydroxyaluminoxane species (HO-AO) acting as Brxc3x8nsted acids. In the formation of such compounds, a cation is derived from the transition, lanthanide or actinide metal compound by loss of a leaving group, and this cation forms an ion pair with an aluminoxate anion devoid of such leaving group. The leaving group is typically transformed into a neutral hydrocarbon thus rendering the catalyst-forming reaction irreversible as shown in Equation 2:
Cp2MXR+HO-AOxe2x86x92[Cp2M-X]⊕(O-AO)xe2x8ax96+RHxe2x80x83xe2x80x83(Eq. 2) 
Note the absence of the leaving group, X, in the anion OAOxe2x8ax96 as compared to the presence of X in the anion, (X-MAO)xe2x8ax96, of Equation 1.
In many of the patents related to the use of aluminoxanes as metallocene co-catalysts, rather broad and generalized assertions have been routinely made regarding aluminum-to-metallocene ratio, types of alkyl aluminoxanes, and ratio of water to aluminum for forming aluminoxanes. However, there is no disclosure of any type that would suggest, let alone demonstrate, the use of an aluminoxane as a Brxc3x8nsted acid to activate metallocenes and related organometallic catalysts. There are, furthermore, no known prior teachings or descriptions of how to use an aluminoxane as a Brxc3x8nsted acid muchless that by so doing it would be possible to reduce the ratio of aluminum to transition, lanthanide or actinide metal to an unprecedentedly low level.
In another of its embodiments the invention of U.S. Pat. No. 6,160,145 provides a process which comprises contacting a transition, lanthanide or actinide metal compound having at least two leaving groups with a hydroxyaluminoxane in which at least one aluminum atom has a hydroxyl group bonded thereto so that one of said leaving groups is lost. As noted above, during the formation of such compounds, an aluminoxate anion is formed that is devoid of the leaving group. Instead the leaving group is typically transformed into a neutral hydrocarbon so that the catalyst forming reaction is irreversible.
Still another embodiment of the invention of U.S. Pat. No. 6,160,145 is a process of polymerizing at least one polymerizable unsaturated monomer, which process comprises contacting said monomer under polymerization conditions with a compound which comprises a cation derived from a transition, lanthanide or actinide metal compound, preferably a metallocene, by loss of a leaving group and an aluminoxate anion derived by transfer of a proton from a stable or metastable hydroxyaluminoxane to said leaving group.
Other embodiments of the invention of U.S. Pat. No. 6,160,145 include catalyst compositions in which a compound comprising a cation derived from a transition, lanthanide or actinide metal compound, preferably a metallocene, by loss of a leaving group and an aluminoxate anion derived by transfer of a proton from a stable or metastable hydroxyaluminoxane to said leaving group is supported on a carrier.
As described in U.S. patent application Ser. No. 09/655,218, filed Sep. 5, 2000 (hereinafter the xe2x80x9c""218 applicationxe2x80x9d), the catalyst compositions described in U.S. Pat. No. 6,160,145 and also herein can have exceptional stability once recovered and maintained under suitable conditions in the absence of a solvent. The ""218 application describes storage of a solid catalyst of this type in a drybox at ambient room temperatures for a one-month period without loss of its catalytic activity. In contrast, the same catalyst composition is relatively unstable if left in the reaction solution or put in solution after it has been removed from solution. The added features of this invention are to recover the catalyst composition (catalytic compound) after its preparation, optionally subject the catalyst composition to one or more finishing procedures and/or optionally mix the catalyst composition with one or more inert substances under suitable inert anhydrous conditions, and store the catalyst composition by itself, in supported form or as a solvent-free mixture with one or more inert substances under suitable conditions which minimize exposure to moisture and air (oxygen) as much as reasonably possible.
Thus in one of the embodiments described in the ""218 application is a compound which comprises a cation derived from d-block or f-block metal compound by loss of a leaving group and an aluminoxate anion derived by transfer of a proton from a stable or metastable hydroxyaluminoxane to said leaving group, wherein such compound is in undissolved form in a dry, inert atmosphere or environment. Preferably the compound in such atmosphere or environment is in isolated form or is in supported form on a catalyst support.
Another embodiment described in the ""218 application is a compound which comprises a cation derived from a d-block or f-block metal compound by loss of a leaving group and an aluminoxate anion devoid of said leaving group, wherein the compound comprised of such cation and aluminoxate anion is in undissolved form in a dry, inert atmosphere or environment. Preferably the compound in such atmosphere or environment is in isolated form or is in supported form on a catalyst support.
A further embodiment described in the ""218 application is a compound which comprises a cation derived from a d-block or f-block metal compound by loss of a leaving group transformed into a neutral hydrocarbon, and an aluminoxate anion derived by loss of a proton from a hydroxyaluminoxane having, prior to said loss, at least one aluminum atom having a hydroxyl group bonded thereto, wherein the compound comprised of such cation and aluminoxate anion is in undissolved form except during one or more optional finishing procedures, if and when any such finishing procedure is performed. In addition, the compound is kept in a dry, inert atmosphere during a storage period. Preferably the compound in such atmosphere or environment is in isolated form or is in supported form on a catalyst support.
The compounds of each of the above embodiments of the ""218 application can be used as a catalyst either in the solid state or in solution. The stability of the compound when in solution is sufficient to enable the compound to perform as a homogeneous catalyst.
Still another embodiment described in the ""218 application is a process which comprises contacting a d-block or f-block metal compound having at least two leaving groups with a hydroxyaluminoxane in which at least one aluminum atom has a hydroxyl group bonded thereto so that one of said leaving groups is lost; recovering the resultant metal-containing compound so formed; and storing such recovered compound (preferably in isolated form or in supported form on a catalyst support) in an anhydrous, inert atmosphere or environment. Such compound is maintained in undissolved form except during one or more optional finishing procedures, if and when any such finishing procedure is performed.
Also provided as another embodiment of the ""218 application is a process which comprises donating a proton from an aluminoxane to a leaving group of a d-block or f-block metal compound to form a compound composed of a cation derived from said metal compound and an aluminoxate anion devoid of said leaving group; recovering the compound composed of such cation and aluminoxate anion; storing such recovered compound (preferably in isolated form or in supported form on a catalyst support) in an anhydrous, inert atmosphere or environment; and maintaining such compound in undissolved form except during one or more optional finishing procedures, if and when any such finishing procedure is performed.
Another embodiment of the ""218 application is a process which comprises interacting a d-block or f-block metal compound having two leaving groups and a hydroxyaluminoxane having at least one aluminum atom that has a hydroxyl group bonded thereto to form a compound composed of a cation through loss of a leaving group which is transformed into a neutral hydrocarbon, and an aluminoxate anion derived by loss of a proton from said hydroxyaluminoxane; recovering the compound composed of such cation and aluminoxate anion; storing such recovered compound (preferably in isolated form or in supported form on a catalyst support) in an anhydrous, inert atmosphere or environment; and maintaining such compound in undissolved form except during one or more optional finishing procedures, if and when any such finishing procedure is performed.
Still other embodiments are described in the ""218 application.
Notwithstanding all of the foregoing advances, the meta-stable nature of the hydroxy groups in the hydroxyaluminoxane species of aluminoxanes can have an negative impact upon the shelf life of this species of compounds. Increasing the steric bulk of these compounds does appear to increase the lifetime of their OH groups (see, e.g., FIG. 6), but not sufficiently to meet the anticipated needs of commercial applications. Storage of these compounds at low temperature, e.g., circa xe2x88x9210xc2x0 C., can significantly increase the compound lifetime (see, e.g., FIG. 7), but cost and operational considerations of this technique also are less that ideal for commercial applications.
Accordingly, a need exists for a way to significantly increasing the lifetime of the OH groups in hydroxyaluminoxanes, preferably at or near room temperature. A need also exists for a facile way to employ olefin polymerization catalysts while avoiding reactor fouling.
The present invention is deemed to meet these and other needs in a surprisingly novel way. It has now been found that hydroxyaluminoxanes can be converted into novel, solid compositions of matter, so as to drastically increase the lifetime of the hydroxy group(s) in the composition (i.e., reduce the composition OH-decay rate), even at room temperature, while at the same time reducing, if not eliminating, reactor fouling.
Thus, one embodiment of this invention provides a composition in the form of one or more individual solids, which composition is formed from components comprised of (i) a hydroxyaluminoxane and (ii) a carrier material compatible with said hydroxyaluminoxane and in the form of one or more individual solids, said composition having a reduced OH-decay rate relative to the OH-decay rate of (i).
This invention also provides in another embodiment a composition which comprises a hydroxyaluminoxane supported on a solid support.
Yet another embodiment of the present invention is a process comprising converting a hydroxyaluminoxane into a composition in the form of one or more individual solids by bringing together (i) a hydroxyaluminoxane and (ii) a carrier material compatible with said hydroxyaluminoxane and in the form of one or more individual solids, whereby the rate of OH-decay for said composition is reduced relative to the rate of OH-decay of (i).
Still another embodiment of the present invention is a supported activated catalyst composition formed by bringing together (A) a composition in the form of one or more individual solids, which composition is formed from components comprised of (i) a hydroxyaluminoxane and (ii) a carrier material compatible with said hydroxyaluminoxane and in the form of one or more individual solids, said composition of (A) having a reduced OH-decay rate relative to the OH-decay rate of (i); and (B) a d- or f-block metal compound having at least one leaving group on a metal atom thereof.
This invention also provides a process of preparing a supported activated catalyst, which process comprises bringing together (A) a composition in the form of one or more individual solids formed by bringing together (i) a hydroxyaluminoxane and (ii) a carrier material compatible with said hydroxyaluminoxane and in the form of one or more individual solids, whereby the rate of OH-decay for said composition is reduced relative to the rate of OH-decay of (i); and (B) a d- or f-block metal compound having at least one leaving group on a metal atom thereof.
In another embodiment of this invention, an olefin polymerization process is provided which comprises bringing together in a polymerization reactor or reaction zone (1) at least one polymerizable olefin and (2) a supported activated catalyst composition which is in accordance with this invention.
Still another embodiment of this invention is a catalyst composition formed by bringing together (A) a hydroxyaluminoxane and (B) rac-ethylenebis(1-indenyl)zirconium dimethyl.
A further embodiment of the invention provides a process for the production of a supported hydroxyaluminoxane which comprises bringing together (i) an aluminum alkyl in an inert solvent, (ii) a water source, and (iii) a carrier material, under hydroxyaluminoxane-forming reaction conditions.
Still another embodiment is a method of forming an olefin polymerization catalyst, which method comprises introducing into a reactor or a reaction zone (A) a hydroxyaluminoxane and (B) a d- or f-block metal compound in proportions such that an active olefin polymerization catalyst is formed. In this embodiment, the hydroxyaluminoxane preferably is fed in the form of (i) a solution of the hydroxyaluminoxane in an inert solvent or in a liquid polymerizable olefinic monomer, or both; (ii) a slurry of the hydroxyaluminoxane in an inert diluent or in a liquid polymerizable olefinic monomer; (iii) unsupported solid particles; or (iv) one or more solids on a carrier material or catalyst support; or (v) any combination of two or more of (i), (ii), (iii), and (iv). More preferably, the hydroxyaluminoxane will be fed in the form of one or more solids on a carrier material suspended in an inert viscous liquid, e.g., mineral oil. Similarly, the d- or f-block metal compound preferably is fed in the form of (i) undiluted solids or liquid, or (ii) a solution or slurry of the d- or f-block metal compound in an inert solvent or diluent, or in a liquid polymerizable olefinic monomer, or in a mixture of any of these. More preferably, the d- or f-block metal compound will be fed in the form of a solution or slurry of the metal compound in an inert solvent or diluent. It is also preferred that the catalyst be formed from only components (A) and (B). The introduction of (A) and (B) into the reactor or reaction zone can proceed in any given order or sequence, or can proceed concurrently. Also, the introduction of (A) and (B) into the reactor or reaction zone can proceed continuously or intermittently. Preferably, the metal compound is fed into the hydroxyaluminoxane, and more preferably the metal compound in the form of a solution or slurry in an inert solvent or diluent will be fed to the hydroxyaluminoxane in the form of one or more solids on a carrier material suspended in an inert viscous liquid.
As another of its embodiments, this invention also provides, in a process for the catalytic polymerization of at least one olefin in a polymerization reaction vessel or reaction zone, the improvement which comprises introducing into the reaction vessel or reaction zone catalyst components comprising (A) a hydroxyaluminoxane and (B) a d- or f-block metal compound, in proportions such that said at least one olefin is polymerized. Components (A) and (B) can be introduced into the polymerization reactor vessel or zone as separate feeds, either continuously or intermittently, and either concurrently or in any sequence. Alternatively, they can be brought together and allowed to interact with each other for a suitable period of time with the resultant composition then being introduced into the polymerization reactor or zone. Other polymerization components, e.g., aluminum alkyl, ordinary hydroxyaluminoxane, etc., can be introduced before, during, or after the introduction of (A) and (B) or either of them or of a preformed catalyst formed by interaction between (A) and (B). The forms in which the hydroxyaluminoxane and the d- or f-block metal compound are fed into the polymerization reactor or zone can be any of those described in the immediately preceding paragraph.
The above and other embodiments, features, and advantages of this invention will become still further apparent from the ensuing description and appended claims.